Phosphorous polymers

ABSTRACT

There is disclosed an amorphous, polymeric material that contains phosphorous, aluminum and carbon atoms, and that is the reaction product of a buffered liquid mixture of a source of phosphorous, such as 85% phosphoric acid, a source of aluminum, such as boehmite, and an organic liquid buffer, such as a carboxylic acid. The polymeric material may be converted to a glassy or crystalline solid by heating to a temperature of at least 150° C., and may be cellulated.

This is a continuation application of Ser. No. 07/630,544, filed on Dec.20, 1990, now abandoned.

RELATED CASE

This application is related to patent application Ser. No. 07/630,813,now abandoned and refiled on Jul. 19, 1991 as a continuation-in-partapplication Ser. No. 07/732,906 now U.S. Pat. No. 5,281,399entitled"REFRACTORY BODY ASSEMBLY". That application is filed of even dateherewith in my name and assigned to the same assignee as thisapplication. The related application is concerned with an assemblywherein a refractory body having multiple gas passageways is positionedwithin a refractory container. The body is spaced from the containerwall by a rigid cellular mass that may be produced from a polymericmaterial in accordance with the invention of this application.

FIELD OF THE INVENTION

The field of the invention is phosphorous-based polymeric materials andtheir production.

BACKGROUND OF THE INVENTION

Organic polymers are based on carbon atoms linked together in chains ofvarying length and structure. These materials are widely used, but theiruse is largely limited to low temperature applications. A great deal ofeffort has been expended in attempts to enhance their thermalresistance. However, these organic materials still tend to degrade, andultimately be destroyed, at relatively low temperatures.

For higher temperature use, interest has centered in glasses andceramics, or in inorganic polymers. Glasses and ceramics can be tailoredto meet most high temperature applications. However, these materialsrequire high melting, or sintering, temperatures, thus rendering themexpensive to produce.

Known inorganic polymers are primarily based on silicon, and arereferred to as silicones. These materials have been developed over thepast half century, and are widely employed in intermediate temperatureapplications. They do not, however, provide the high temperature serviceavailable with glasses and ceramics.

The present invention provides a family of polymeric materials based onphosphorous. These polymers are basically inorganic in nature, but alsohave an associated organic group. They are of particular interestbecause they can be formed at room temperature, and then thermallyconverted to a glass or crystalline state. However, the conversion is ata temperature well below that normally required to melt a glass.Further, the phosphorous polymers may have additives that provide a widerange of glasses or crystalline phases.

SUMMARY OF THE INVENTION

My invention resides in an amorphous, polymeric material containingphosphorous, aluminum and carbon atoms. In the preferred method formaking my inventive material, it is the reaction product of a bufferedliquid system composed essentially of a source of phosphorous, a sourceof aluminum, and an organic liquid buffer. The system may furthercontain a variety of modifying additives, including both organic andinorganic materials. In one specific embodiment, nitrogen may beincorporated by adding a nitrogen containing material, such as urea. Inanother, halogens may be incorporated as halides. In other embodiments,a source of an oxide, such as silica, boric oxide, ceria, titania,zirconia, alkaline earth and alkali metal oxides, and transition metaloxides, may be incorporated in the system. The generally preferredsource of phosphorous is 85% phosphoric acid. Also, relatively inertfillers and reinforcing media may be included.

The invention further resides in a method of producing an amorphous,inorganic polymeric material containing phosphorous, aluminum and carbonatoms, the preferred method comprising mixing a source of aluminum witha source of phosphorous oxide in an organic liquid buffered system. Thatmethod may further include heating the material to a temperature of atleast 150° C. to produce a glassy or crystalline material.

PRIOR ART

In addition to the general knowledge of polymers already referred to,attention is directed to the following United States Patents:

U.S. Pat. No. 3,547,670. (Fuchs et al.) describes hard, adhesive bindersand coatings for metal, glass, ceramic, or refractory surfaces. Thebinders and coatings are produced from a mixture of one part by weight(pbw) superphosphoric acid (101 to 108% H₃ PO₄) and 0.02 to 0.10 pbwglassy phosphate with alumina in an amount to provide an Al₂ O₃ :P₂ O₅mole ratio of about 2:3 to 3:1. The mixture is thermally cured on thesurface involved, and may optionally contain silica and titania asadditives. The glassy phosphate is a premelted sodium phosphate glassthat may contain CaO and Al₂ O₃. It is described as a criticalingredient to moderate the vigorous exothermic reaction.

U.S. Pat. No. 3,372,110 (Fuchs) describes the production of the glassyphosphate component used in the Fuchs et al. patent, above.

U.S. Pat. No. 3,736,176 (Francel et al.) describes coating a glasssurface by spraying an aqueous solution on a hot glass surface and heatfusing the coating. The solution contains water, aluminum phosphate,phosphoric acid and a selected phosphate, oxide, carbonate, nitrate, orhalide. There is no indication of a polymer mixture.

U.S. Pat. No. 3,223,537 (Wiegert et al.) discloses adding 22-27 parts ofphosphoric acid to a mixture of 8-14 parts water; 25-31 parts granularalumina, 30-40 parts granular aluminum hydroxide and 0.01-0.1 partsaluminum powder to produce a foamed product.

U.S. Pat. No. 3,261,696 (Wiegert et al.) is a continuation-in-part thatdiscloses adding alumina to a zirconia mixture. This mixture contains76-80 parts zirconia, 7.5-10 parts alumina and 0.1-0.2 parts aluminumpowder to which is added 3.1-5.0 parts water and 8-10 parts phosphoricacid to cause foaming.

U.S. Pat. No. 3,382,082 (Eubanks et al.) discloses producing afoamed-in-place body by pouring a slurry of a composition into a mold tofoam and be cured at 65°-100° C.. The composition includes 39-60 partsphosphoric acid, 10-55 parts aluminum hydroxide, 0.1-0.5 parts aluminumpowder, 0.7-4.0 parts bentonite and sufficient aluminum phosphate tomake up 100 parts in the mixture.

U.S. Pat. No. 3,762,935 (Leach) states that the foams disclosed in theEubanks et al. patent are subject to collapse. To correct this, 1-20% ofglass frit is added, and the foamed body is heated to a temperature inthe range of 1000°-2000° C. This causes the glass to deposit on the cellwalls of the foam and strengthen the walls.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 in the appended drawing are graphical illustrations ofcrystal structure, and lack thereof, respectively. The FIGURES are basedon x-ray diffraction (XRD) data and compare a crystalline mineral,boehmite, with an amorphous polymer produced therefrom in accordancewith the invention.

DESCRIPTION OF THE INVENTION

The present invention is predicated on my discovery that phosphorous, inthe form of an oxide or phosphate, can be combined with a source ofaluminum and a source of carbon to form a stable, amorphous polymer.

The source of aluminum may be the oxide, although a hydrated, orhydroxide, form is preferred. The hydroxide may be one of the mineralforms, such as, bauxite, boehmite, diaspore, gibbsite, bayerite, ornordstrondite, aluminum chlorohydrate, Al₂ (OH)3Cl.2.5H₂ O, is anotherpreferred source. The aluminum source should be added last, withvigorous stirring, since the reaction is strongly exothermic and usuallyaccompanied by a large increase in viscosity. In fact, when alumina isadded to phosphoric acid in the absence of a buffer, the reactionproceeds so vigorously that the mixture almost immediately sets up toform a rigid mass. This precludes any mixing, casting, or otherprocessing.

Any source of phosphorous may be employed. However, a phosphate isnormally used. Commercial 85% phosphoric acid is preferred because ofits ready availability. However, other phosphates, such as aqueoussolutions of ammonium mono-, or di-, basic phosphate, or a metalphosphate, such as calcium phosphate, may be employed, providing theadditional ions are desired, or may be tolerated. The ammoniumphosphates may be desirable as a solvent where boric oxide is to beincorporated in the polymeric material.

An organic liquid buffer is a preferred source of carbon and may be anyof the known and commercially available organic compounds. Thus, it may,for example, be selected from one or more of the following organicgroups: alkanes, alkenes, alkynes, aromatics, alcohols, ethers, carbonylcompounds, carboxylic acids and esters, amines and amides, monomers andpolymers. Aliphatic acids, such as acetic and tartaric, are particularlyeffective. However, other organics, such as beta-alanine, ethyleneglycol and EDTA may be employed, depending on the particularcharacteristics desired. For example, beta-alanine is also a goodsolvent for boric oxide.

By varying the stoichiometries of the starting materials, polymers maybe produced having viscosities that range from very thin to semisolidsthat approach a brittle state at ambient temperature. In general,viscosity increases with the mole ratio of Al₂ O₃ to P₂ O₅ which, forthat reason, should not normally exceed about 1:1. Also, depending onthe proportions, as well as the components used, particularly theorganic, the polymers may be opaque, translucent, or transparent.

X-ray studies show these mixtures to be amorphous as made.Fourier-Transform Infra Red (FT-IR) analyses show that the materialshave structures that are totally different from their precursormaterials. The polymeric nature is also evidenced by the fact thatviscosity continuously changes as a function of mixing time. That is,the viscosity increases as the mixing time increases.

The change effected by the method of the invention is illustrated in theappended drawing. The FIGURES of the drawing show XRD curves. These arebased on data obtained by scanning a material as it is rotated in anautomated powder diffraction unit available from North American PhilipsCorp. and designated Model 3720. The scanning angle, in the customaryunits of Two Theta, is plotted along the horizontal axis, whileintensity, in terms of counts/seconds (cps), is plotted along thevertical axis.

FIG. 1 represents data obtained from scanning a sample of the mineralboehmite (aluminum hydroxide) as received. The several intensity peaksare characteristic of the mineral. These peaks occur at values of 6.47,6.38, 3.181, 2.353, 2.341, 1.857, 1.453 and 1,437.

FIG. 2 represents data obtained from scanning a film of a viscouspolymer sample dried on a microscope slide. The polymer is that obtainedfrom Example 1, infra. Noteworthy is the essential flatness of, and lackof peaks in, the curve. This is typical of an amorphous material free ofcrystals, such as crystal-free glass or polymer.

Nitrogen may be introduced into the polymer by addition of organicnitrogen sources, such as urea or amines. This tends to stiffen, orrender more viscous, the polymer. However, it may also provide a clearwater white, transparent polymer that has excellent light transmission.This may find application as an intermediate between glass sheets inwindows, doors, and the like. An application of considerable interest isfire doors, since the polymer also foams when heated.

It is also possible to incorporate halogens into the polymeric product.This may be accomplished by such additives as metal chlorides. However,a less stable additive, such as an ammonium halide or an organic halidemay be more effective.

It is also contemplated that any of the known inert fillers and/orreinforcing media may be added. This is particularly important in afoamed product where added strength may be highly significant. Thus,such known reinforcing forms as whiskers, fibers, and plates may beemployed. Materials ranging from glass fibers to silicon carbidewhiskers are contemplated.

The polymeric materials of the invention may provide a host for knownorganic lasing dyes. These may be added during the formation of thematerial, or by subsequent addition if the viscosity is sufficient.Thus, a material containing a dye may possess interestingopto-electronic properties.

Most phosphate glass and crystalline stoichiometries may be formulatedby combining a source of one or more suitable metal oxides in thepolymeric mixture. In particular, such oxides as boric oxide, silica,ceria, titania, zirconia, the alkaline earth and alkali metal oxides andtransition metal oxides may be incorporated. The alkali metal oxides,which tend to produce water-soluble glasses, should be employed withcare to avoid such instability. Phyllosilicates, such as vermiculite,may also be added to the mixture.

To produce a glass and/or glass-ceramic material, the polymer mixture isheated to a temperature well below the normal melting temperature forsuch a composition. Depending on the precursor constituents of thepolymeric material and the thermal treatment conditions employed, eithera glass or crystalline body may be produced. In general, if thepolymeric material has a composition that tends to crystallize, and isheated gradually, formation of a crystalline material is favored. Properselection of the composition and/or very rapid heating, such as placingthe material in a preheated furnace, tends to produce a glassy body.

In producing the polymeric mixture, the mole ratio of alumina tophosphate (Al₂ O₃ :P₂ O₅) , should not exceed about 1:1. As indicatedearlier, viscosity decreases as the excess of phosphoric acid increases.

It is also possible to produce a foamed body from the polymeric materialof the invention. The basic, three-component system will produce a rigidaluminophosphate matrix for the cells of the foam. The matrix may beglassy or crystalline depending on the makeup of the precursor polymer,and the nature of the foaming process. In the case of a glassy matrix,the aluminophosphate may be modified by the presence of knownglassmaking, or modifying, materials. In the case of a crystallizedmatrix, a second crystal phase, in addition to the aluminophosphate, mayresult from the presence of one or more oxides selected from: silica,boric oxide, ceria, titania, zirconia, the transition metal oxides andthe alkali and alkaline earth metal oxides.

A foamed body may be produced by heating the amorphous polymeric productin a confined space to a relatively low temperature, and holding at thattemperature to permit a desired degree of gas evolution. The temperaturemay be as low as 150° C., but this normally requires a long hold timewith consequent loss of gas. Accordingly, a temperature of about 300°C., and a hold time of one hour, are usually preferred.

For example, the polymeric product of a buffered system, composed of onemole tartaric acid, two moles each of aluminum hydroxide and boricoxide, and four moles of 85% phosphoric acid, was heated to 300° C. andheld for one hour. This resulted in a hard, foamed body which showedaluminophosphate and borophosphate crystal phases when examined by x-raydiffraction.

The foamed body may be heated to much higher temperatures, of course,with no structural change. However, in some cases, a change in crystalphase may occur.

Proper selection of the precursor materials for the polymeric productwill permit producing a rigid body, either solid or foamed, that may beeither transparent to, or absorptive of, microwave radiation.

In the former case, the material may be employed as a container or moldfor a material to be heated by microwaves. In the latter case, wheremicrowaves are absorbed, the material may be tailored to function as asusceptor. The presence of alkali metals favor absorption. Conversely,for good microwave transmission, such metals should be avoided.

Normally, a thermal treatment is carried out in air, the atmosphere notaffecting the generation of a foamed or solid body. However, it iscontemplated that the treatment may be in a static or flowing atmosphereof a reactive gas if a special effect is desired. Thus, an oxygen orhydrogen atmosphere may be employed if, respectively, an oxidized orreduced surface is desired. Other reactive atmospheres include ammonia,sulfides and the halogens. Conversely, an inert atmosphere, such asargon or helium, may be employed if possible reaction is to be avoided.

SPECIFIC EXAMPLES

The invention is further illustrated by reference to several specific,representative embodiments. In each example, the relative amounts ofmaterials involved are presented in mole ratios, unless otherwiseindicated.

EXAMPLES 1-6

Six formulations of acetic acid (HAC), aluminum hydroxide (AlOOH) and85% phosphoric acid (H₃ PO₄) were prepared by adding the AlOOl H to amixture of acetic and phosphoric acids. TABLE 1 shows the mole ratios ofthe three materials for the six formations. It also shows the nature ofthe product produced. In each case, a vigorous exothermic reaction tookplace, and the mixtures were continually stirred.

                  TABLE 1                                                         ______________________________________                                        HAC      AlOOH     H.sub.3 PO.sub.4                                                                      Appearance                                         ______________________________________                                        1.   1       1         3     transparent viscous                              2.   1       2         3     Very hard, white, opaque                         3.   1       1         1     Very hard, white, opaque                         4.   1       2         4     Very hard, white, opaque                         5.   1       1         4     Fluid transparent                                6.   1       1         2     Viscous, white, opaque                           ______________________________________                                    

It is apparent that the viscosity of the polymeric reaction product isdependent on the relative proportions of aluminum hydroxide andphosphoric acid in the parent mixture. Thus, an increase in the relativecontent of aluminum hydroxide increases the viscosity, while increasingthe relative content of phosphoric acid decreases viscosity. It is mybelief, based on FT-IR analyses of the polymerized product, thataluminum actually enters a polymeric structure. Whatever the phenomenoninvolved, the increase in viscosity, as well as changes in x-ray andFT-IR patterns, suggest development of a polymeric material containingboth aluminum and phosphorous.

EXAMPLE 7-24

In each of these examples, a three component mixture was produced in themanner described above for Examples 1-6. However, the liquid organicbuffer was varied, as were the relative proportions of the mixtureingredients. The polymeric products obtained varied in viscosity in thesame manner as noted for Examples 1-6.

In each case, the polymeric reaction product was subsequently heated ata rate of about 300° C./hour to a predetermined temperature, held atthat temperature for one hour, and cooled. The atmosphere maintainedover the material during the heat treatment was either air or ammoniagas. The fired product in each case was a foam material that wasanalyzed for crystal phases by x-ray diffraction (XRD) techniques.

TABLE 2, below, shows, for each example, the organic buffer used; theratio, in moles, of organic: AlOOH:H₃ PO₄ ; the hold temperature in °C.and time in hours; the atmosphere; and the crystal phase(s) observed byX-ray.

The organic buffers utilized included tartaric, oxalic, citric, acrylicand formic acids, as well as ethylene glycol, urea, β-alanine and EDTA.

                  TABLE 2                                                         ______________________________________                                                               Temp./                                                 No.  Organic  Ratio    Time   Atmos.                                                                              Crystal                                   ______________________________________                                        7.   β-  1:1:3    300/1  NH.sub.3                                                                            NH.sub.4 AlP.sub.2 O.sub.7                     Alanine                        Al(PO.sub.3).sub.3                        8.   β-  1:1:3    900/1  Air   Al(PO.sub.3).sub.3                             Alanine                        AlPO.sub.4                                9.   Tartaric 1:1:3    300/1  Air   AlH.sub.2 P.sub.3 O.sub.10 xH.sub.2                                           O                                         10.  Tartaric 1:1:2    300/1  Air   AlPO.sub.4                                11.  Tartaric 1:1:2    300/1  NH.sub.3                                                                            AlPO.sub.4                                12.  Oxalic   1:1:2    300/1  NH.sub.3                                                                            NH.sub.4 AlP.sub.2 O.sub.7                                                    AlPO.sub.4                                13.  Oxalic   1:1:2    600/1  NH.sub.3                                                                            (NH.sub.4).sub.6 (PO.sub.3).sub.6                                             H.sub.2 O                                                                     Al(PO.sub.3).sub.3                        14.  Formic   1:1:2    300/1  NH.sub.3                                                                            AlPO.sub.4                                                                    NH.sub.4 AlP.sub.2 O.sub.7                15.  Formic   1:1:2    600/1  NH.sub.3                                                                            Al(PO.sub.3).sub.3                                                            H.sub.2 AlP.sub.3 O.sub.10                16.  Formic   1:1:2    300/1  Air   AlH.sub.2 P.sub.3 O.sub.10 XH.sub.2                                           O                                         17.  Formic   1:1:3    300/1  Air   AlH.sub.2 P.sub.3 O.sub.10 xH.sub.2                                           O                                         18.  EDTA     1:0.5:3.5                                                                               300/16                                                                              Air   Al(PO.sub.3).sub.3                        19.  Citric   1:1:3    300/1  Air   AlH.sub.2 P.sub.3 O.sub.10 xH.sub.2                                           O                                         20.  Ethylene 1:1:1    300/1  Air   AlPO.sub.4                                     Glycol                                                                   21.  Ethylene 1:1:1    600/1  Air   AlPO.sub.4                                     Glycol                                                                   22.  Ethylene 1:1:1    900/1  Air   AlPO.sub.4                                     Glycol                                                                   23.  Urea     1:1:2.4  300/1  NH.sub.3                                                                            Glass                                     24.  Acrylic  1:1:3    300/1  Air   AlH.sub.2 P.sub.3 O.sub.10 xH.sub.2       ______________________________________                                                                            O                                     

EXAMPLE 25

Sixty (60) grams of acetic acid were mixed with 236 grams of 85%phosphoric acid. Thirty (30) grams of boehmite (AlOOH) were added withstirring, together with 50 grams of talc. The reaction product washeated to 300° C. in air and held at that temperature one hour. Thisproduced an eggshell-like foam that bonded to a glass surface. XRDanalysis showed a crystal phase corresponding to Al₃ (PO₄)₂ (OH)₃.5H₂ O.Further heating to 600° C. produced an amorphous transparent soft foam.Heating to 900° C. for one hour produced a glassy foam that bonded tocordierite and that remained a glassy foam when exposed to water at 95°C. for one hour.

EXAMPLE 26

Sixty (60) grams of acetic acid were mixed with 354 grams of 85%phosphoric acid and 100 grams of calcium acetate. Sixty grams ofboehmite were added slowly with constant stirring. When the mixture washeated to 300° C. and held for an hour, a firm grey foam resulted thatshowed an AlPO₄ crystal phase. Heating to 600° C. produced a crystallinegrey foam, while heating to 900° C. produced a hard white foam showingAlPO₄ and Al(PO₃)₃ phases.

EXAMPLE 27

Sixty (60) grams of acetic acid were mixed with 354 grams of 85%phosphoric acid, sixty (60) grams of magnesium acetate and sixty (60)grams of urea. To this mixture were added sixty (60) grams of boehmitewith constant stirring. Heating for an hour at 300° C. in air produced afirm tan foam. This foam was amorphous with a trace of AlPO₄ crystals,and floated when placed on water at 95° C.. Further heating at 600° C.changed the foam color to grey. At 900° C. the color became white, andhexagonal aluminum and magnesium phosphate crystal phases were observed.

EXAMPLE 28

Sixty (60) grams of acetic acid were mixed with 354 grams of 85% H₃ PO₄and 120 grams of urea. To the mixture, 120 grams of boehmite were addedwith constant stirring. Heating for an hour at 300° C. produced a firmtan foam which remained visually unchanged when heated an hour at 600°C. Heating to 900° C. changed the foam to a hard, off-white materialthat showed a cubic aluminum phosphate phase. The foam floated whenplaced on water at 95° C.

EXAMPLES 29-32

Fifty (50) grams of calcium acid phosphate (Ca(H₂ PO₄)₂.H₂ O) weredissolved in 50 ml. of nitric acid (HNO₃). Forty (40) ml. of 2M tartaricacid and twelve (12) grams of B(OH)₃ were added to the solution, afterwhich twelve (12) grams of Al(OH)₃ were added with stirring. When thereaction subsided, a viscous gel remained.

The gel was then subjected to four (4) separate heat treatments in air.The product of each heat treatment was analyzed by powder XRD. The TABLEthat follows shows the heat treatments in terms of heating rate and holdtime, and the nature of the product.

                  TABLE                                                           ______________________________________                                        Heat Treatment      Product                                                   ______________________________________                                        1.     Dried at 110° C.                                                                        Amorphous                                             2.     300°/hr. to 600° C.                                                              Hard, white foam,                                            Hold one hour    Slight crystallization                                3.     300° C./hr to 1000° C.                                                           Hard white foam with                                         Hold one hour    Ca.sub.2 P.sub.2 O.sub.7 and                                                  CaO.P.sub.2 O.sub.5.B.sub.2 O.sub.3                                           Crystal phases.                                       4.     300° C./hr to 1200° C.                                                           Hard white foam with                                         Hold one hour    Ca.sub.2 P.sub.2 O.sub.7 Crystal                      ______________________________________                                                                phase.                                            

EXAMPLE 33

A buffered mixture was prepared by mixing tartaric acid, boehmite powder(aluminum hydroxide), anhydrous boric acid B(OH)₃ and 85% phosphoricacid in a mole relation of 1:2:2:4, respectively. The mixture wascontinually stirred with the boehmite added last. When the reactionsubsided, a viscous liquid remained. This was placed in an oven at 300°C. and held for one hour. The foamed body thus produced was about threetimes the height of the precursor gel. It had a bulk density of about0.3 grams/cm³ and a coefficient of thermal expansion (25°-600° C.) ofabout 69×10⁻⁷ /°C.

EXAMPLE 34-45

Numerous experiments were carried out to illustrate the variety ofmaterials that might be included in the phosphorous polymer, bufferedliquid system as additives. Also, the effect of such additions on thebulk density of foams produced from the polymer was measured. The1:2:2:4 buffered mixture, used and described in the previous example,was employed as a base formulation. A further fifth component wasincluded in this formulation for each experiment. The amount was apercentage by weight of the, base.

In each case, the resulting polymeric material was heated to 600° C.,held at that temperature for one hour in air and cooled. TABLE I, below,lists, in weight percent, some of the additives employed; also, the bulkdensity, in grams/cubic centimeter (g/cm³), of the foam produced, andthe appearance of the foam.

                  TABLE I                                                         ______________________________________                                        Additive        Bulk Density                                                                             Appearance                                         ______________________________________                                        34.   5% CaCl.sub.2 0.273      Hard, Black                                    35.  10% CaCl.sub.2 0.255      Hard, Black                                    36.  20% CaCl.sub.2 0.548      Hard, Grey                                     37.  10% Ca(H.sub.2 PO.sub.4).H.sub.2 O                                                           0.244      Glassy inclusion                               38.  10% NH.sub.4 BF4                                                                             0.213      Hard, Grey                                     39.  10% NaMoO.sub.4.2H.sub.2 O                                                                   0.349      Hard, Bluish, White                            40.  10% NAWO.sub.4.2H.sub.2 O                                                                    0.51       Hard, Eggshell                                 41.  10% Zn.sub.3 (PO.sub.4).sub.2.2H.sub.2 O                                                     0.212      Hard, Grey                                     42.  10% BaCl.sub.2.2H.sub.2 O                                                                    0.44       Glassy surface                                 43.  10% Bone Ash   0.28       Coarse, Grey                                                                  Slightly glassy.                               44.  10% BaHPO.sub.4                                                                              0.43       Coarse, Dull Black                             45.  10% AlF.sub.3  0.32       Hard                                           ______________________________________                                    

In general, the space occupied by the mixture before foaming increasedby about three to five times during foaming. This indicated a decreasein density to about 35 to 20% of the original polymeric material.

EXAMPLE 46-52

Examples 1 and 5 illustrate formulations that provide a transparentpolymerized product. Several other formulations have providedtransparent, or translucent gels. These gels have remained stable overseveral months' exposure to ambient conditions. Particularly effectiveare gels produced with urea or ethylene glycol as the organic buffer.

The following TABLE shows several formulations, in terms of mole ratiosof phosphoric acid: organic: aluminum hydroxide, that producedtransparent or translucent gels. The TABLE lists mole ratio and theorganic in each example.

                  TABLE                                                           ______________________________________                                        Mole ratio    Organic     Appearance                                          ______________________________________                                        46.   1:1:1       Urea        Transparent                                     47.   3:1:1       Ethylene glycol                                                                           Transparent                                     48.   1:1:1       Ethylene glycol                                                                           Transparent                                     49.   3:1:1       Beta-alanine                                                                              Transparent                                     50.   2:1:1:1     Tartaric acid                                                                             Transparent                                                       + boric acid                                                51.   1:1:1:1     Tartaric acid                                                                             Translucent                                                       + 40% SiO.sub.2 sol                                         52.   1:1:1:1     Oxalic acid Translucent                                                       + 40% SiO.sub.2 sol                                                                       Translucent                                     ______________________________________                                    

EXAMPLES 53-56

Four (4) comparison mixtures were prepared to demonstrate how organicadditions modify the reactions and working properties ofalumina-phosphate mixtures. In each mixture, the components were mixedin equal mole ratios, that is 1:1 or 1:1:1.

In one mixture, powdered boehmite (Al100H) was added to 85% phosphoricacid. The reaction was very vigorous with a strong exothermic output,and the mixture set up to a stiff body immediately. This prevented anystirring, casting, shaping, or other working of the reaction product.

The procedure was repeated, except that the phosphoric acid ingredientwas commercial 85% phosphoric acid from which water had been removed toproduce 100% acid. The reaction, and product produced, were essentiallythe same as with the 85% acid.

Again, the procedure was repeated. This time, the powdered boehmite wasadded to a buffered system composed of equal molar parts of 85%phosphoric acid and glacial acetic acid. The reaction was stillexothermic, but much less vigorous. This provided a gel-like materialthat could be stirred, and from which fibers could be drawn and shapesmolded. However, the viscosity continuously increased as the reactionproceeded with stirring, eventually resulting in a hard, white, opaquematerial.

The foregoing procedure was repeated, except that the 100% phosphoricacid was substituted for the 85% acid. The resulting reaction, andproperty characteristics of the product, were essentially the same.However, the reaction proceeded at a slightly slower rate.

The conclusions to be drawn were two-fold. First, organic liquid bufferadditions were necessary to slow down the reaction and provide usefulworking properties, as well as optimum physical-chemical properties.Second, the continuing increase of viscosity as the reaction progressedin the buffered systems, and the grey (off-white) color obtained whenthe material was heated to 600° C., made it apparent that polymerizationwas occurring.

I claim:
 1. An amorphous polymeric material produced by mixing andreacting the following components:(a) an inorganic compound containing aphosphorus atom; (b) an inorganic compound containing an aluminum atom,the phosphorus-containing compound and the aluminum-containing compoundbeing present in amounts to provide a molar ratio of Al₂ O₃ :P₂ O₅ thatdoes not exceed 1:1; in (c) an organic liquid buffer, said organicliquid buffer consisting essentially of at least one organic groupselected from the group consisting of alkanes, alkenes, alkyls,aromatics, alcohols, ethers, carbonyls, carboxylic acids and esters,amines and amides, monomers and polymers; with, optionally, (d) aninorganic compound containing at least one metal oxide selected from thegroup consisting of silica, boric oxide, titania, zirconia, ceria,alkaline earth and alkali metal oxides, transition metal oxides, and asource of halogen.
 2. A polymeric material in accordance with claim 1wherein the phosphorus-containing compound is a phosphate or phosphoricacid.
 3. A polymeric material in accordance with claim 2 wherein thephosphoric acid is 85% phosphoric acid.
 4. A polymeric material inaccordance with claim 1 wherein the aluminum-containing compound isaluminum hydroxide or aluminum chlorohydrate.
 5. A polymeric material inaccordance with claim 4 wherein the aluminum hydroxide is the mineralboehmite.
 6. A polymeric material in accordance with claim 1 wherein theorganic liquid buffer is a carboxylic acid.
 7. A polymeric material inaccordance with claim 6 wherein the acid is tartaric acid.
 8. Apolymeric material in accordance with claim 1 wherein the organic liquidbuffer includes urea whereby a nitrogen is introduced into the polymer.9. A polymeric material in accordance with claim 1 wherein the organicliquid buffer is ethylene glycol.
 10. A polymeric material in accordancewith claim 1 wherein the oxide is boric oxide.
 11. A polymeric materialin accordance with claim 1 that additionally contains a reinforcingmedium in the form of whiskers, fibers or plates.
 12. A polymericmaterial in accordance with claim 1 wherein the material is transparent.13. A polymeric material in accordance with claim 1 which contains anorganic lasing dye to impart opto-electronic properties.
 14. Anamorphous polymeric material in accordance with claim 1 wherein thephosphorus-containing compound is selected from the group consisting ofphosphorus oxides, phosphorus acids, and phosphates, and thealuminum-containing compound is selected from the group consisting ofaluminum oxide, aluminum hydroxide, and hydrated aluminum compounds.